Antibacterial Fibers and Materials

ABSTRACT

Antimicrobial fibers that include antimicrobial nanoparticles dispersed substantially uniformly in a polymer matrix. Textiles and other materials can be formed from such fibers. The fibers may be formed via a masterbatch process or in a process wherein the antimicrobial nanoparticles, polymeric component, and additive(s) are melt processed together directly. Devices can be at least partially formed from polymer materials that include antimicrobial nanoparticles dispersed substantially uniformly in a polymer matrix.

The present disclosure claims priority on U.S. Provisional PatentApplication Ser. No. 62/740,121 filed Oct. 2, 2018; 62/749,280 filedOct. 23, 2018; and 62/837,956 filed Apr. 24, 2019, all of which areincorporated herein by reference.

The present disclosure relates to antimicrobial materials and methodsfor making the same. In one non-limiting application of the disclosure,there is provided antimicrobial fibers, methods of manufacturing thesame, and articles including the antimicrobial fibers. Moreparticularly, the antimicrobial fibers include antimicrobialnanoparticles substantially uniformly dispersed in a polymer matrix and,even more particularly, the antimicrobial fibers include metalantimicrobial nanoparticles substantially uniformly dispersed in apolymer matrix. In another non-limiting application of the disclosure,there is provided a device that is at least partially formed of apolymer material that includes antimicrobial nanoparticles substantiallyuniformly dispersed in a polymer matrix.

BACKGROUND ON THE DISCLOSURE

With rising living standards, people are paying more attention to theirhealth. Many commonly used items such as clothing, towels, mops, sheets,pillow cases, shoes, caps, hats, gloves, and the like carry a largenumber of microorganisms. For microorganisms in nature, the skinprovides a barrier to undesirable microorganisms. In general, someresident bacteria on the skin plays a role in protecting the skin fromundesirable microorganisms. However, a small number of those undesirablemicroorganisms can multiply on and through the skin, respiratory tract,digestive tract, and/or genital tract mucosa and potentially cause harmto an individual. Textiles, in the nature of human wear, come intocontact with sweat, sebum and other human secretions, and are alsocontaminated by environmental exposures (e.g., dirt, food, smoke, etc.)which can also spread pathogens. Antibacterial products are a controlmeans to inhibit bacterial growth and repress bacterial reproduction,which protect the human body from the invasion of foreign microbialactivities. At present, it is common to use physical antimicrobialproducts to contact and destroy common microbial components.

The existing antibacterial textiles are divided into two maincategories. The first kind of antimicrobial textile is processed (i.e.,the antimicrobial agent is added) after the textile has been formed orfinished. This process is widely used because of its simplicity,suitability with a large number of antimicrobial agents, and wideapplicability. Surface coating, resin finishing, or microencapsulationof the textile are commonly used in such a process. The antimicrobialmaterial is typically distributed on the surface of fibers and fabrics.

Although this type of antibacterial textile is commonly used, thesetreated textiles do not adequately maintain antibacterial effectivenessafter continuous washing and reuse because the antimicrobial materialtends to fall off or be removed after one or more washing or uses of thetextiles. In some cases, almost all of the antibacterial effectivenessis lost (e.g., antibacterial fibers no longer have antibacterialproperties) after only a few uses or washes.

The second kind of antibacterial textile is made from antibacterialfibers. Permanent antibacterial fibers show greater advantages than thefinished antibacterial textiles. Inorganic antibacterial agents haveattracted much attention due to their long effectiveness. Inorganicantibacterial agents have different antibacterial effectiveness. Forantibacterial metals, the order of antibacterial activity is:Hg>Ag>Cd>Cu>Zn>Fe>Ni. However, antibacterial activity alone is not theonly criteria for use in a fiber since some metals can be harmful to thehuman body. For example, mercury, cadmium, and lead have antibacterialproperties, but they are harmful to the human body. The order of safetyfor metal ions is: Ag>Co>Ni>Al>Zn>Cu═Fe>Mn>Sn>Ba>Mg>Ca. Therefore, whenconsidering the safety and antimicrobial properties, silver is the bestand calcium is the least desirable of the non-toxic metals. Currentlysilver, zinc and copper have found preference in textiles. However, thecolor of copper can affect the performance of the product. Silver islimited in use due to its easy oxidation and discoloration, high price,and tendency to high agglomeration.

In addition to textiles, other items that are commonly in contact withhuman skin (such as children's toys, toothbrush handles, razorbladehandles, brush handles, etc.) have been treated to reduce bacterialgrowth Typically, these devices are coated with an antibacterial coatingwhich, like textile coatings, typically wears off after a period oftime. Some devices have included metal salts incorporated into a polymermaterial; however, such salts generally do not disperse properly in theplastic, thereby limiting the effectiveness of the antibacterialproperties of the device.

Zinc is internationally recognized as a “safety” material. The changesof surface electron and crystal structure of fine zinc nanoparticlegrains will produce surface and volume effects, quantum size, andmacro-tunneling effects which macro-objects do not have. Zinc alsoexhibits excellent photo-catalytic, UV-shielding, antibacterial andphotoluminescence properties. Zinc has shown important application valuein the fields of ceramics, chemical industry, environmental protection,optoelectronics, biology, and medicine.

Because zinc can inhibit the growth of bacteria, viruses, and fungi, andpromote the metabolism of human skin, zinc-based antibacterial fibershave good antibacterial properties and are healthy for the skin. Zinc isalso an essential trace element for the human body. Zinc particles havemany positive characteristics, such as high stability (non-oxidation,non-color, non-toxic, tasteless), low dosage, high antibacterialefficiency, safety, non-toxic, and long antibacterial effectiveness.Zinc has passed the toxicity test of SGS, European Compulsory Standard(ROHS), acute toxicity oral test, skin irritation test, skin allergytest and Japanese Industrial Standard (JIS) antibacterial test. Zinc ishighly safe, non-toxic, harmless, non-irritating, and has no allergicreaction to the human body.

Nanometer inorganic antibacterial agents have excellent antibacterialproperties and small particle size. However, nano-powders are very fine,easy to agglomerate, have poor compatibility with fiber resins and othertypes of polymers, and are very difficult to uniformly disperse in aformed fiber or polymer device.

In view of the current state of the art, there is a need for a polymerfiber or polymer device that can be formed with a nanoparticleantibacterial agent, when such nanoparticle antibacterial agent isevenly disbursed throughout the polymer fiber or polymer device.

BRIEF DESCRIPTION OF THE DISCLOSURE

The present disclosure relates to antimicrobial materials such as fibersor devices, methods of manufacturing the same, and articles includingthe antimicrobial fibers or devices.

In one non-limiting aspect of the disclosure, there is providedantimicrobial fibers that include antimicrobial nanoparticlessubstantially uniformly dispersed in a polymer matrix and, even moreparticularly, the antimicrobial fibers include metal antimicrobialnanoparticles substantially uniformly dispersed in a polymer matrix. Asdefined herein, “antimicrobial fibers having substantially uniformlydispersed antimicrobial nanoparticles in a polymer matrix” means that 1)a certain volume (e.g., 150-1000 cubic microns and all values and rangestherebetween) of the fiber is located in different locations of thefiber, such certain volumes will have 60-100% (and all values and rangestherebetween) of the same weight percent of antimicrobial nanoparticles,and 2) 50-100% (and all values and ranges therebetween) of theantimicrobial nanoparticles in such certain volume are spaced apart fromone another. As such, if two different sections of a fiber having thesame volume were cut off and analyzed, the first analyzed section wouldhave 60-167 wt. % of the particles in the second analyzed section, andfor both the first and second analyzed sections, 50-100% of theantimicrobial nanoparticles in such sections will be spaced apart fromone another. In one non-limiting embodiment, the antimicrobial fibers,for a certain volume of the fiber in different locations, has within70-100% of the same weight percent of antimicrobial nanoparticles and atleast 60% of the antimicrobial nanoparticles in such certain volumes arespaced apart from one another; typically, for a certain volume of thefiber in different locations, has within 80-100% of the same weightpercent of antimicrobial nanoparticles and at least 70% of theantimicrobial nanoparticles in such certain volumes are spaced apartfrom one another; more typically, for a certain volume of the fiber indifferent locations, has within 80-100% of the same weight percent ofantimicrobial nanoparticles and at least 75% of the antimicrobialnanoparticles in such certain volumes are spaced apart from one another;and still more typically, for a certain volume of the fiber in differentlocations, has within 90-100% of the same weight percent ofantimicrobial nanoparticles and at least 90% of the antimicrobialnanoparticles in such certain volumes are spaced apart from one another.

The size of the antimicrobial nanoparticles are generally no more than200 nanometers, and typically about 10-200 nanometers (and all valuesand ranges therebetween), more typically about 10-150 nanometers, stillmore typically 25-120 nanometers, and even more typically 50-100nanometers.

The fibers can be used as a partial or full substitute for thread and/orfabric that is used to form articles such as, but not limited to,clothing, bedding, towels, cloths, rags, mops, shoes and other types offootwear, caps, hats, luggage, purses, backpacks, carrying cases,furniture fabric, curtains, awnings, tents, umbrellas, furniture covers,grill covers, laundry containers, storage containers, rugs, carpeting,pillow covers, blankets, throws, seat covers, bandages, straps, rope,twine, yarn, string, gowns, scrubs, masks, bandages, dressings, pillows,life jackets, bathmats, pads, diapers, wipes, sleeping bags, pet beds,pet toys, canvas products, and any other device or material that isfully or partially formed from threads and/or fabric.

In another non-limiting aspect of the disclosure, there are provideantimicrobial devices in which antimicrobial nanoparticles aresubstantially uniformly dispersed in a polymer matrix and, even moreparticularly, the antimicrobial devices include metal antimicrobialnanoparticles substantially uniformly dispersed in a polymer matrix.Such devices are generally molded, extruded, 3D printed, etc. As definedherein, “antimicrobial device having substantially uniformly dispersedantimicrobial nanoparticles in a polymer matrix” means that for acertain volume of the polymer device (e.g., 150-1000 cubic microns andall values and ranges therebetween) that includes the antimicrobialnanoparticles in different locations, such certain volumes will havewithin 60-100% (and all values and ranges therebetween) of the sameweight percent of antimicrobial nanoparticles and 50-100% (and allvalues and ranges therebetween) of the antimicrobial nanoparticles insuch certain volume will be spaced apart from one another. The devicecan be any type of device that is at least partially formed of a polymermaterial wherein it is desirable to inhibit or prevent bacteria growthon the outer surface of all or a portion of the device. Non-limitingdevices include, but are not limited to, healthcare-related products(e.g., furniture, flooring, medical devices, light fixtures, brushes,combs, beds, eating utensils, wheelchairs or other patient transportdevices, crutches, walking aids, toilet seats, wash basins, wash basinhardware, door handles, wall panels, doors or door panels, trash bags,trash cans or receptacles, shower curtains, containers, counter tops,TVs and other appliances, clocks and other electronic devices, etc.);transportation-related products (e.g., seats, floorings, cabin walls,masks, eating utensils, toilet seats, shower curtains, wash basins, washbasin hardware, door handles, wall panels, doors or door panels, trashbags, trash cans or receptacles, security containers or other types ofcontainers, security scanning equipment, counter tops, TVs and otherappliances, clocks and other electronic devices, picture frames, etc.);hotel/motel-related products (e.g., furniture, carpet, sheets, bathmats,shower curtains, light fixtures, brushes, combs, bathrobes, toiletseats, wash basins, wash basin hardware, door handles, wall panels,doors or door panels, trash bags, trash cans or receptacles, containers,counter tops, TVs and other appliances, clocks and other electronicdevices, picture frames and other types of frames, pens and otherwriting implements, etc.); military-related products (clothing, masks,furniture, flooring, light fixtures, curtains, footwear, brushes, combs,beds, eating utensils, toilet seats, wash basins, wash basin hardware,door handles, wall panels, doors or door panels, trash bags, trash cansor receptacles, containers, counter tops, TVs and other appliances,clocks and other electronic devices, walls and other structures, lifejackets, weapons, communication equipment, etc.); building-relatedproducts (e.g., flooring, roofing, wall panels, windows, grout, tile,counter tops, carpeting, furniture, toilet seats, wash basins, washbasin hardware, door handles, wall panels, doors or door panels, trashbags, trash cans or receptacles, containers, counter tops, TVs and otherappliances, clocks and other electronic devices, walls and otherstructures, paints, sealants, surface protectants, etc.);cosmetic-related products; personal healthcare-related products;athletic products (e.g., pads, helmets, grips, shoes, sports equipment,etc.); personal electronic devices (e.g., cell phones, TVs, stereos,clocks, keyboards, computers, headphones, 3D eyewear, game consoles,game controllers, projectors, printers, scanners, displays, 3D printers,etc.); infant and children and adult products (e.g., diapers, furniture,toys, strollers, cribs, pacifiers, baby bottles, sippy cups, teethingrings, diaper pails, crib rockers, bikes, transportation devices, babycarriers, car seats, furniture, sheets, footwear, brushes, combs, beds,etc.); other products (e.g., food storage products, pet beds, pet toys,hunting gear, towels, sponges, cleaning brushes and plungers, bath mats,shower curtains, shelf liners, bread boxes, trash cans, trash bags,shoes, shoe inserts, luggage, backpacks, purses, wallets, belts, etc.).In essence, any polymer material can container the antimicrobialtechnology of the present disclosure.

Non-limiting antimicrobial nanoparticles include one or more metalmaterials selected from the group of zinc metal, copper metal, silvermetal, iron metal, zinc oxide, copper oxide, silver oxide, iron oxide,and/or salts of zinc, copper, silver, and/or iron. In one particularnon-limiting embodiment, the antimicrobial nanoparticles include or arefully formed of zinc metal, salts of zinc, and/or zinc oxide. In anotherparticular non-limiting embodiment, the antimicrobial nanoparticlesinclude or are fully formed of zinc metal and/or zinc oxide. In anotherparticular non-limiting embodiment, the antimicrobial nanoparticlesinclude or are fully formed of zinc metal. When the antimicrobialnanoparticles include or are fully formed of metal, the purity of themetal is at least about 90%, typically have a purity of at least about98%, more typically have a purity of at least about 99%, and even morehave a purity of at least about 99.95%. Generally, the metal used as theantimicrobial nanoparticle is a single metal; however, it can be a metalalloy that includes two or more of zinc metal, copper metal, silvermetal, iron metal (e.g., Zn—Cu alloy, Zn—Ag alloy, Ag—Cu alloy, Fe—Agalloy, Fe—Zn alloy, etc.).

In accordance with one non-limiting embodiment of the presentdisclosure, thread, yarn, fabric and/or textile is partially or fullyformed of antimicrobial fibers. One or more of the antimicrobial fibersincludes a polymer matrix and antimicrobial nanoparticles dispersedsubstantially uniformly throughout the polymer matrix.

In accordance with one non-limiting embodiment of the presentdisclosure, a device can be formed that is partially or fully formed ofan antimicrobial polymer material. The antimicrobial polymer materialincludes a polymer matrix and antimicrobial nanoparticles dispersedsubstantially uniformly throughout the polymer matrix.

In accordance with another non-limiting embodiment of the presentdisclosure, there is provided an antimicrobial fiber with anon-circular-shaped cross section that includes antimicrobialnanoparticles dispersed substantially uniformly throughout the polymermatrix. As can be appreciated, the cross-sectional shape of theantibacterial fibers can be circular. In one non-limiting embodiment,the antimicrobial fibers of the present disclosure have a non-circularcross-sectional shape (e.g., clover-shaped, cross-shaped, fibers havingone or more grooves along the outer surface and length of the fiber,etc.). Such a non-circular cross-sectional shape can be used to improvemoisture absorption properties, quick drying properties, breathabilityproperties, flexibility properties, and/or resilience properties of theantimicrobial fiber as compared to circular-shaped cross section fibers.

In accordance with another non-limiting embodiment of the presentdisclosure, there is provided a method for forming antimicrobial fiberswhich includes forming spun antimicrobial fibers from a spinning heatedmixture, wherein the heated mixture includes one or more antimicrobialnanoparticles, one or more polymeric components, and at least oneadditive selected from the group of one or more surfactants and/or oneor more coupling agents. The mixture can optionally include othermaterials (e.g., colorant, aromatic material for smell, mica to makefiber feel cool, tourmaline to make fiber feel warm, thinning agent,etc.). The surfactant and/or coupling agent facilitate in the uniformdispersion of the nanoparticles in the heated mixture so that the formedfibers have a uniform dispersion of the antimicrobial nanoparticles inthe formed fibers. The thinning agent (when used) is generally used toobtain a desired viscosity of the heated mixture for purposes of propermixing and/or proper formation of the fibers. The thinning agent can beor include water and/or some other neutral liquid. In one non-limitingapplication, the surfactant and/or coupling agent also facilitate ininhibiting the agglomeration of the antimicrobial nanoparticles in theheated mixture and to also inhibit the agglomeration of theantimicrobial nanoparticles to the formed fibers. Generally, a formedfiber that includes antimicrobial nanoparticles will contain less than10 vol. % agglomerated antimicrobial nanoparticles having an averagesize that is greater than 2 micrometers. In non-limiting configuration,a formed fiber that includes antimicrobial nanoparticles will containless than 5 vol. % agglomerated antimicrobial nanoparticles having anaverage size that is greater than 2 micrometers. In non-limitingconfiguration, a formed fiber that includes antimicrobial nanoparticleswill contain less than 5 vol. % agglomerated antimicrobial nanoparticleshaving an average size that is greater than 1.75 micrometer. Innon-limiting configuration, a formed fiber that includes antimicrobialnanoparticles will contain less than 5 vol. % agglomerated antimicrobialnanoparticles having an average size that is greater than 1.5micrometers. In non-limiting configuration, a formed fiber that includesantimicrobial nanoparticles will contain less than 2 vol. % agglomeratedantimicrobial nanoparticles that have an average size of greater than1.5 micrometers. In non-limiting configuration, a formed fiber thatincludes antimicrobial nanoparticles will contain less than 1 vol. %agglomerated antimicrobial nanoparticles that have an average size ofgreater 1.5 micrometers. In non-limiting configuration, a formed fiberthat includes antimicrobial nanoparticles will contain less than 0.5vol. % agglomerated antimicrobial nanoparticles that have an averagesize of greater than 1.5 micrometers.

In accordance with another non-limiting embodiment of the presentdisclosure, the surfactants can be anionic surfactants, cationicsurfactants and/or non-ionic surfactants. Non-limiting surfactants thatcan be used in the present disclosure include, but are not limited to,stearic acid, sodium dodecyl sulfonate surfactants, quaternary ammoniumsurfactants, amino acid surfactants, betaine surfactants, fatty acidglyceride ester surfactants, fatty acid sorbitan surfactants, lecithinsurfactants, and/or Tween™ series surfactants (e.g., polyethoxylatedsorbitan ester surfactants, nonionic polyoxyethylene surfactants, etc.).

In accordance with another non-limiting embodiment of the presentdisclosure, there is provided a method for forming a masterbatch from amelted mixture that comprises one or more antimicrobial nanoparticles,one or more polymeric components, and at least one additive selectedfrom the group of one or more surfactants and/or one or more couplingagents, by cooling the mixture and optionally granulating the mixture toform the masterbatch. Other materials can optionally be used to form thefinal masterbatch (e.g., colorant, aromatic material for smell, mica tomake fiber feel cool, tourmaline to make fiber feel warm, etc.). Theseother materials, other than possibly the thinning agent (when used), areselected to at least partially remain in the final fiber. When athinning agent is optionally used to form the final solid or granulatedmasterbatch, the thinning agent is generally removed from the finalmasterbatch by evaporation, degradation, etc. Generally, less than 2% ofthe thinning agent remains in the final solid or granulated masterbatch,typically less than 1% of the thinning agent remains in the final solidor granulated masterbatch, more typically less than 0.5% of the thinningagent remains in the final solid or granulated masterbatch, still moretypically less than 0.1% of the thinning agent remains in the finalsolid or granulated masterbatch, and yet more typically less than 0.01%of the thinning agent remains in the final solid or granulatedmasterbatch.

In accordance with another non-limiting embodiment of the presentdisclosure, there is provided a method for forming antimicrobial fiberswhich includes the step of extruding and/or spinning a heated mixture ofa masterbatch and additional polymeric component, wherein themasterbatch includes a mixture of one or more types of antimicrobialnanoparticles, one or more polymeric components, and at least oneadditive selected from the group of one or more surfactants and/or oneor more coupling agents. During the final formation of the antimicrobialfiber, generally at least about 80%, and typically about 90-100% of theadditives are burned off, degraded, or are otherwise removed from thefinal formed antimicrobial fiber. Other materials can optionally be usedto form the final masterbatch (e.g., thinning agent, colorant, aromaticmaterial for smell, mica to make fiber feel cool, tourmaline to makefiber feel warm, etc.). These other materials, other than possibly thethinning agent (when used), are selected to at least partially remain inthe final fiber. When a thinning agent is optionally used to form thefinal solid or granulated masterbatch, the thinning agent is generallyremoved from the final masterbatch by evaporation, degradation, etc.Generally, less than 2% of the thinning agent remains in the final solidor granulated masterbatch, typically less than 1% of the thinning agentremains in the final solid or granulated masterbatch, more typicallyless than 0.5% of the thinning agent remains in the final solid orgranulated masterbatch, still more typically less than 0.1% of thethinning agent remains in the final solid or granulated masterbatch, andyet more typically less than 0.01% of the thinning agent remains in thefinal solid or granulated masterbatch.

In accordance with another non-limiting embodiment of the presentdisclosure, there is provided an antimicrobial fiber that has asubstantially uniform dispersion of antimicrobial nanoparticles in thefiber, and wherein such fiber retains its antibacterial effectivenessafter many standard wash cycles (i.e., a standard wash cycle in acommercially available household washing machine for about 20-60 minutesat water temperatures of 20-70° C. and wherein commercially availablehousehold washing detergent that is approved for the commerciallyavailable household washing machine may or may not be used). Aftertesting by independent testing institutions, the antibacterialeffectiveness of the antimicrobial fiber of the present disclosureagainst Escherichia coli (E. coli), Staphylococcus aureus (S. aureus),and Candida albicans (C. albicans) after one wash was at least 90% theantibacterial effectiveness of the unwashed antimicrobial fiber. In onenon-limiting embodiment, the antibacterial effectiveness of theantimicrobial fiber of the present disclosure against E. coli, S.aureus, and C. albicans after one standard wash cycle was at least 95%the antibacterial effectiveness of the unwashed antimicrobial fiber, andmore typically the antibacterial effectiveness of the antimicrobialfiber of the present disclosure against E. coli, S. aureus, and C.albicans after one standard wash cycle was at least 99% theantibacterial effectiveness of the unwashed antimicrobial fiber. In onenon-limiting embodiment, the antibacterial effectiveness of theantimicrobial fiber of the present disclosure against E. coli, S.aureus, and C. albicans after 100 standard wash cycles was at least 85%the antibacterial effectiveness of the unwashed antimicrobial fiber,typically the antibacterial effectiveness of the antimicrobial fiber ofthe present disclosure against E. coli, S. aureus, and C. albicans after100 standard wash cycles was at least 90% the antibacterialeffectiveness of the unwashed antimicrobial fiber, more typically theantibacterial effectiveness of the antimicrobial fiber of the presentdisclosure against E. coli, S. aureus, and C. albicans after 100standard wash cycles was at least 95% the antibacterial effectiveness ofthe unwashed antimicrobial fiber, and yet more typically theantibacterial effectiveness of the antimicrobial fiber of the presentdisclosure against E. coli, S. aureus, and C. albicans after 100standard wash cycles was at least 98% the antibacterial effectiveness ofthe unwashed antimicrobial fiber. During the testing of the fibers, thefibers were washed in pure water, and in water that included a standardconsumer washing machine detergent and the temperature of the water wasset at all common temperature settings for consumer washing machines.The antimicrobial fiber was also tested for irritation to skin; noevidence of irritation occurred for prewashed and post-washed fibers.The antibacterial fibers of the present disclosure have goodantibacterial effect and durable antibacterial property, as well as goodhygroscopicity, fast drying resistance, ultraviolet resistance,softness, resilience, and smoothness. At the same time, chemicalmodification of the nanoparticles (e.g., forming metal salts or metaloxides) is not required.

In accordance with another non-limiting embodiment of the presentdisclosure, there is provided an antimicrobial fiber that has asubstantially uniform dispersion of antimicrobial nanoparticles in thefiber, and wherein such fiber retains its antibacterial effectivenessafter many washes, and wherein less than 1% of the antimicrobialnanoparticles in the fiber leaches from the fiber after the fiber issubjected to one standard wash cycle (i.e., a standard wash cycle in acommercially available household washing machine for at least 20 minutesat water temperatures of 20-70°, and wherein commercially availablehousehold washing detergent that is approved for the commerciallyavailable household washing machine may or may not be used). In onenon-limiting embodiment, less than 1% of the antimicrobial nanoparticlesin the fiber leaches from the fiber after the fiber is subjected to 100standard wash cycles. In another non-limiting embodiment, less than 0.1%of the antimicrobial nanoparticles in the fiber leaches from the fiberafter the fiber is subjected to one standard wash cycle. In anothernon-limiting embodiment, less than 0.1% of the antimicrobialnanoparticles in the fiber leaches from the fiber after the fiber issubjected to 100 standard wash cycles.

In accordance with another non-limiting embodiment of the presentdisclosure, there is provided a method for forming an antimicrobialdevice which includes molding, extruding, etc., a heated mixture to forman antimicrobial device, wherein the heated mixture includes one or moretypes of antimicrobial nanoparticles, one or more polymeric components,and at least one additive selected from the group of one or moresurfactants and/or one or more coupling agents. Additional materials canbe optionally used in the mixture (e.g., thinning agent, colorant,aromatic material for smell, etc.). The surfactant and/or coupling agentare used to facilitate in the uniform dispersion of the nanoparticles inthe heated mixture so that the formed device has a substantially uniformdispersion of the antimicrobial nanoparticles. In one non-limitingapplication, the surfactant and/or coupling agent are also used tofacilitate in inhibiting the agglomeration of the antimicrobialnanoparticles in the heated mixture and also inhibit the agglomerationof the antimicrobial nanoparticles in the formed device.

In accordance with another non-limiting embodiment of the presentdisclosure, there is provided a method for forming a masterbatch from amelted mixture that comprises one or more antimicrobial nanoparticles,one or more polymeric components, and at least one additive selectedfrom the group of one or more surfactants and/or one or more couplingagents, by cooling the mixture and optionally granulating the mixture toform the masterbatch. Additional materials can be optionally used in themixture (e.g., thinning agent, colorant, aromatic material for smell,etc.).

In accordance with another non-limiting embodiment of the presentdisclosure, there is provided a method for forming an antimicrobialdevice which includes the step of 1) molding, extruding, etc., a heatedmixture of a masterbatch and additional polymeric component, wherein themasterbatch includes a mixture of one or more types of antimicrobialnanoparticles, one or more polymeric components, and at least oneadditive selected from the group of one or more surfactants, and/or oneor more coupling agents. During the final formation of the antimicrobialdevice, generally at least about 80%, and typically about 90-100% of theadditives are burned off, degraded, or otherwise removed from the finalformed antimicrobial device. Additional materials can be optionally usedin the mixture (e.g., thinning agent, colorant, aromatic material forsmell, etc.). These other or additional materials, other than possiblythe thinning agent, are designed to remain in the final formedantimicrobial device.

One non-limiting object of the disclosure is the provision of a textilecomprising antimicrobial fibers, wherein at least one of theantimicrobial fibers includes a polymer matrix and antimicrobialnanoparticles dispersed substantially uniformly throughout the polymermatrix.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the substantially uniform dispersion ofthe antimicrobial nanoparticles in the antimicrobial fibers at leastpartially a result of a mixture of a) polymer used to form the polymermatrix, b) the antimicrobial nanoparticles, and c) a surfactant and/orcoupling agent included in the mixture prior to the formation of saidantimicrobial fibers.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the mixture includes both surfactant andcoupling agent.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the antimicrobial nanoparticles includeone or more metal materials selected from the group of zinc metal,copper metal, silver metal, iron metal, zinc oxide, copper oxide, silveroxide, iron oxide, zinc salt, copper salt, silver salt, and iron salt.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the polymer used to form the polymermatrix includes one or more polymer materials selected from the groupconsisting of a polyester, a polyamide, a polyolefin, a polycarbonate,and an acrylonitrile butadiene styrene polymer.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the polymer used to form said polymermatrix includes polyester, and the polyester includes polyethyleneterephthalate.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the antimicrobial nanoparticles have amedian particle size of less than or equal to 0.1 μm.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the antimicrobial nanoparticles have amedian particle size of about 50-200 nm.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the antimicrobial fibers comprise about0.5-12 wt. % of the antimicrobial nanoparticles.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the antimicrobial fibers have a crosssection shape selected from the group consisting of a clover, cross,hollow cylinder, triangle, and dumbbell.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the mixture includes surfactant.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the surfactant includes one or morecompounds selected from the group consisting of stearic acid, sodiumdodecyl sulfonate surfactants, quaternary ammonium surfactants, aminoacid surfactants, betaine surfactants, fatty acid glyceride estersurfactants, fatty acid sorbitan surfactants, lecithin surfactants, andTween™ series surfactants.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the mixture includes coupling agent.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the coupling agent includes a silaneand/or titanate coupling agent.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the coupling agent includes one or morecompounds selected from the group consisting of silane coupling agentA-150, silane coupling agent A-151, silane coupling agent A-171, silanecoupling agent A-172, silane coupling agent A-1100, and silane couplingagent. Agent A-187, silane coupling agent A-174, silane coupling agentA-1891, silane coupling agent A-189, silane coupling agent A-1120,silane coupling agent KH-550, silane coupling agent KH-560, silanecoupling agent KH-570, silane coupling agent KH-580, silane couplingagent KH-590, silane coupling agent KH-902, silane coupling agentKH-903, silane coupling agent KH-792, phenyltrimethoxysilane,phenyltriethoxysilane, methyltriethoxysilane, titanate coupling agent101, titanate coupling agent 102, and titanate coupling agent 105.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the antimicrobial fibers include mica,colorant, tourmaline, and/or aromatic material.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the textile is in the form of, but notlimited to, the group consisting of a clothing, bedding, towels, cloths,rags, mops, shoes and other types of footwear, caps, hats, luggage,purses, backpacks, carrying cases, furniture fabric, curtains, awnings,tents, umbrellas, furniture covers, grill covers, laundry containers,storage containers, rugs, carpeting, pillow covers, blankets, throws,seat covers, bandages, straps, rope, twine, yarn, string, gowns, scrubs,masks, bandages, dressings, pillows, life jackets, bathmats, pads,diapers, wipes, sleeping bags, pet beds, pet toys, canvas products, andany other device or material that is fully or partially formed fromthreads and/or fabric.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the textile is at least partially formedfrom threads of material, and wherein at least a plurality of thethreads used to at least partially form the textile includes saidantimicrobial fibers, and wherein threads that include the antimicrobialfibers formed of at least 10 wt. % of said textile.

Another and/or alternative non-limiting object of the disclosure is theprovision of a textile wherein the threads are formed of at least 30 wt.% of the antimicrobial fibers.

Another and/or alternative non-limiting object of the disclosure is theprovision of a method for forming antimicrobial fibers, wherein themethod includes spinning a heated mixture to form spun antimicrobialfibers, and wherein the heated mixture includes antimicrobialnanoparticles, polymeric component, and at least one additive selectedfrom the group consisting of surfactant and coupling agent.

Another and/or alternative non-limiting object of the disclosure is theprovision of a method for forming antimicrobial fibers furthercomprising the step of winding, stretching, and/or cooling the spunfibers.

Another and/or alternative non-limiting object of the disclosure is theprovision of a method for forming a masterbatch for use in mixing withanother polymer to form an antimicrobial fiber, wherein the methodincludes a) blending a mixture comprising antimicrobial nanoparticles, apolymeric component, and at least one additive selected from the groupconsisting of surfactants and coupling agents, and b) granulating saidblended mixture to form granulated pieces of the masterbatch.

Another and/or alternative non-limiting object of the disclosure is theprovision of a method for forming a masterbatch for use in mixing withanother polymer to form an antimicrobial fiber wherein the step ofblending is at a temperature of about 100-350° C.

Another and/or alternative non-limiting object of the disclosure is theprovision of a method for forming a masterbatch for use in mixing withanother polymer to form an antimicrobial fiber wherein the antimicrobialnanoparticles constitute about 4-49 wt. % of the masterbatch, and thepolymeric component constitutes about 40-95 wt. % of the masterbatch.

Another and/or alternative non-limiting object of the disclosure is theprovision of a method for forming a masterbatch for use in mixing withanother polymer to form an antimicrobial fiber wherein at least oneadditive constitutes about 0.001-30 wt. % of the masterbatch.

Another and/or alternative non-limiting object of the disclosure is theprovision of a method for forming antimicrobial fibers, wherein themethod includes a) extruding a mixture comprising masterbatch particlesand polymer particles, and b) spinning the extruded mixture into spunfibers; and wherein the masterbatch particles comprise antimicrobialnanoparticles, a masterbatch polymer, and at least one additive selectedfrom the group consisting of surfactants and coupling agents.

Another and/or alternative non-limiting object of the disclosure is theprovision of a method for forming antimicrobial fibers wherein the stepof extruding is at a temperature about 200-350° C.

Another and/or alternative non-limiting object of the disclosure is theprovision of a method for forming antimicrobial fibers wherein themixture comprises about 2-20 wt. % of the masterbatch particles andabout 80-98 wt. % of the polymer particles.

Another and/or alternative non-limiting object of the disclosure is theprovision of a method for forming antimicrobial fibers furthercomprising the step of winding, stretching, and/or cooling said spunfibers.

Another and/or alternative non-limiting object of the disclosure is theprovision of an antimicrobial thread comprising antimicrobial fibers andnon-antimicrobial fibers, and wherein the antimicrobial fibersconstitute about 15-90 wt. % of the antimicrobial thread, and thenon-antimicrobial fibers constitute about 10-85 wt. % of theantimicrobial thread, and wherein the antimicrobial fibers formed of apolymer matrix having antimicrobial nanoparticles are dispersedsubstantially uniformly throughout said polymer matrix, and wherein thesubstantially uniform dispersion of the antimicrobial nanoparticles inthe antimicrobial fibers is at least partially a result of a mixture ofa) polymer used to form the polymer matrix, b) antimicrobialnanoparticles, and c) surfactant and/or coupling agent prior to theformation of the antimicrobial fibers, and wherein the non-antimicrobialfibers include one or more materials selected from the group consistingof cotton fibers, wool fibers, silk fibers, linen fibers, hemp fibers,flax fibers, rayon fibers, polyester fibers, nylon fibers, mylar fibers,glitter fibers and metallic fibers, and wherein the non-antimicrobialfibers are absent antimicrobial nanoparticles.

Another and/or alternative non-limiting object of the disclosure is theprovision of an antimicrobial thread wherein less than 1% of theantimicrobial nanoparticles in the antimicrobial fibers leach from theantimicrobial fibers after the antimicrobial thread has been subjectedto one standard wash cycle.

Another and/or alternative non-limiting object of the disclosure is theprovision of an antimicrobial thread wherein less than 1% of theantimicrobial nanoparticles in the antimicrobial fibers leach from theantimicrobial fibers after the antimicrobial thread has been subjectedto 100 standard wash cycles.

Another and/or alternative non-limiting object of the disclosure is theprovision of an antimicrobial thread wherein the antimicrobial fibersafter the antimicrobial thread has been subjected to one standard washcycle retains at least 90% of an antibacterial effectiveness as comparedto the antimicrobial fibers prior to being subjected to a standard washcycle.

Another and/or alternative non-limiting object of the disclosure is theprovision of an antimicrobial thread wherein the antimicrobial fibersafter the antimicrobial thread has been subjected to 100 standard washcycles retains at least 90% of an antibacterial effectiveness ascompared to the antimicrobial fibers prior to being subjected to astandard wash cycle.

These and other objects and advantages will become apparent from thediscussion of the distinction between the disclosure and the prior artand when considering the preferred embodiment shown in the accompanyingdrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

Reference may now be made to the drawings, which illustrate variousembodiments that the disclosure may take in physical form and in certainparts and arrangements of parts wherein:

FIG. 1 is a magnified photograph of a plurality of antimicrobial fibersin accordance with some non-limiting embodiments of the presentdisclosure;

FIG. 2 is a perspective drawing of an antimicrobial fiber in accordancewith some non-limiting embodiments of the present disclosureillustrating the substantially uniform dispersion of the antimicrobialnanoparticles in the antimicrobial fiber;

FIG. 3 is an annotated scanning electron microscope (SEM) image ofantimicrobial fibers in accordance with some non-limiting embodiments ofthe present disclosure illustrating the substantially uniform dispersionof the antimicrobial nanoparticles in the antimicrobial fiber and alsoillustrating that most, if not all, of the individual antimicrobialnanoparticles and any agglomerated antimicrobial nanoparticles are lessthan 2 micrometers in size;

FIGS. 4-7 are SEM images of antimicrobial fibers in accordance with somenon-limiting embodiments of the present disclosure illustrating thesubstantially uniform dispersion of the antimicrobial nanoparticles inthe antimicrobial fiber and also illustrating that most, if not all, ofthe individual antimicrobial nanoparticles and any agglomeratedantimicrobial nanoparticles are less than 2 micrometers in size;

FIG. 8 is a flowchart illustrating a non-limiting method for formingantimicrobial fibers in accordance with some non-limiting embodiments ofthe present disclosure; and

FIG. 9 is a flowchart illustrating another non-limiting method forforming antimicrobial fibers in accordance with some non-limitingembodiments of the present disclosure.

DETAILED DESCRIPTION OF NON-LIMITING EMBODIMENTS

A more complete understanding of the articles/devices, processes, andcomponents disclosed herein can be obtained by reference to theaccompanying drawings. These figures are merely schematicrepresentations based on convenience and the ease of demonstrating thepresent disclosure, and are, therefore, not intended to indicaterelative size and dimensions of the devices or components thereof and/orto define or limit the scope of the exemplary embodiments.

Although specific terms are used in the following description for thesake of clarity, these terms are intended to refer only to theparticular structure of the embodiments selected for illustration in thedrawings and are not intended to define or limit the scope of thedisclosure. In the drawings and the following description below, it isto be understood that like numeric designations refer to components oflike function.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise.

As used in the specification and in the claims, the term “comprising”may include the embodiments “consisting of” and “consisting essentiallyof.” The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that require thepresence of the named ingredients/steps and permit the presence of otheringredients/steps. However, such description should be construed as alsodescribing compositions or processes as “consisting of” and “consistingessentially of” the enumerated ingredients/steps, which allows thepresence of only the named ingredients/steps, along with any unavoidableimpurities that might result therefrom, and excludes otheringredients/steps.

Numerical values in the specification and claims of this applicationshould be understood to include numerical values which are the same whenreduced to the same number of significant figures and numerical valueswhich differ from the stated value by less than the experimental errorof conventional measurement technique of the type described in thepresent application to determine the value.

All ranges disclosed herein are inclusive of the recited endpoint andindependently combinable (for example, the range of “from 2 grams to 10grams” is inclusive of the endpoints, 2 grams and 10 grams, and all theintermediate values).

The terms “about” and “approximately” can be used to include anynumerical value that can vary without changing the basic function ofthat value. When used with a range, “about” and “approximately” alsodisclose the range defined by the absolute values of the two endpoints,e.g. “about 2 to about 4” also discloses the range “from 2 to 4.”Generally, the terms “about” and “approximately” may refer to plus orminus 10% of the indicated number.

Percentages of elements should be assumed to be percent by weight of thestated element, unless expressly stated otherwise.

Referring now to the drawings, FIG. 1 is a photograph showing an endview of a plurality of antimicrobial fibers in accordance with somenon-limiting embodiments of the present disclosure. The depictedantimicrobial fibers have a non-circular cross section shape and includeantibacterial nanoparticles substantially uniformly dispersed throughouta polyester matrix.

FIG. 2 is a perspective drawing of an antimicrobial fiber 10 inaccordance with some non-limiting embodiments of the present disclosure.The fiber 10 includes a plurality of antimicrobial nanoparticles 20 thatare substantially uniformly dispersed throughout a polymer matrix 30.

FIG. 3 is an annotated SEM image of a portion of a fiber in accordancewith some non-limiting embodiments of the present disclosure. The sizeof the nanoparticles can be compared to the size graph. The size graphhas 10 segments wherein each segment represents 1 micrometers. Theaverage size of the nanoparticles is less than 200 nanometers and theaverage size of any agglomerated nanoparticles in the fiber is typicallyless than 1-2 micrometers, and typically less than 1 micrometer.

As noted in FIG. 3, the plurality of antibacterial nanoparticles aresubstantially uniformly dispersed in the fiber. Such a dispersion of theantimicrobial nanoparticles inhibits or prevents the antimicrobialnanoparticles from falling off the fiber and permits more wash cyclesduring the lifetime of a textile that is formed of or includes theantimicrobial fibers. Additionally, the shape of the antimicrobial fiberhas a relatively high surface area compared to circular-shaped crosssection fibers. The higher surface area has been found to acceleratesdrying.

FIGS. 4-7 are additional SEM images of antimicrobial fibers inaccordance with some non-limiting embodiments of the present disclosure.As is illustrated in FIG. 4-7, the size of the nanoparticles can becompared to the size graph. The size graph has 10 segments wherein eachsegment represents 2 micrometers. The average size of the nanoparticlesis less than 200 nanometers and the average size of any agglomeratednanoparticles in the fiber is typically less than 1-2 micrometers, andtypically less than 1 micrometer.

Referring now to FIG. 8, there is illustrated a flowchart for a methodfor forming antibacterial fibers in accordance with some non-limitingembodiments of the present disclosure. The method 100 includes forming amasterbatch 110 containing antimicrobial nanoparticles (e.g., zincnanoparticles, etc.), polymeric component (e.g., polyester, PET, PA,PBT, PP, Aramid, PE, PC, ABS, etc.), and one or more additives. Thepolymeric component typically constitutes about 40-94 wt. % of themasterbatch (and all values and ranges therebetween). The antimicrobialnanoparticles typically constitute about 5-49 wt. % of the masterbatch(and all values and ranges therebetween), typically 10-40 wt. %antimicrobial nanoparticles, and more typically 20-38 wt. % (e.g. 25 wt.%, 20-38 wt. %, 30 wt. % etc.) antimicrobial nanoparticles. Typically,the weight ratio of the antimicrobial nanoparticles to the polymericcomponent in the masterbatch is 15:80 to 40:55 (and all values andranges therebetween). Generally, the one or more polymeric components inthe masterbatch constitute the largest weight percent of components thatform the masterbatch.

The masterbatch can be formed of a single type of polymeric component orbe formed of two or more different polymeric components. Theantimicrobial nanoparticles in the masterbatch can be a single type ofantimicrobial nanoparticle or be formed of two or more different typesof antimicrobial nanoparticles. In one non-limiting embodiment, theantimicrobial nanoparticles are formed partially or fully of zinc metalnanoparticles. The size and shape of the antimicrobial nanoparticles inthe masterbatch can be the same or different.

The one or more additives include surfactant and/or coupling agent(e.g., a silane coupling agent). The one or more additives in themasterbatch generally constitute about 0.002-30 wt. % of the masterbatch(and all values and ranges therebetween), typically 0.002-18 wt. %additive, and more typically about 0.002-12 wt. % additive. Whensurfactant is included as an additive in the masterbatch, the surfactantgenerally constitutes about 0.001-20 wt. % of the masterbatch (and allvalues and ranges therebetween), typically about 0.001-12 wt. %, andmore typically about 0.001-8 wt. %. When a coupling agent is included asan additive in the masterbatch, the coupling agent generally constitutesabout 0.001-20 wt. % of the masterbatch (and all values and rangestherebetween), typically about 0.001-12 wt. %, and more typically about0.001-8 wt. %. The amount of surfactant and coupling agent in themasterbatch can the same or different. When the additive includes bothsurfactant and coupling agent, the weight ratio of the surfactant to thecoupling agent is about 1:1.5 to 1.5:1 (and all values and rangestherebetween). In one non-limiting embodiment, equal amounts of couplingagent and surfactant are added to the masterbatch.

The masterbatch can potentially include other materials (e.g., thinningagent, colorant, mica, tourmaline, etc.). Mica can be added to improvethe softness and texture of the fiber and to make the fiber feel cool tothe touch. When mica is added, it generally constitutes 0.1-15 wt. % ofthe masterbatch (and all values and ranges therebetween), typically 2-12wt. %, and more typically 6-10 wt. %. When colorant is used, thecolorant generally includes 0.01-3 wt. % of the masterbatch (and allvalues and ranges therebetween). Tourmaline can be added to make thefiber feel warmer to the touch. When tourmaline is added, it generallyconstitutes 0.1-15 wt. % of the masterbatch (and all values and rangestherebetween), and typically 2-12 wt. %. Thinning agent can be used toreduce the viscosity of the melted masterbatch. When thinning agent isadded, it generally constitutes 0.1-25 wt. % of the masterbatch (and allvalues and ranges therebetween), and typically 1-15 wt. %.

Non-limiting examples of formulations that are used to form themasterbatch in accordance with the present disclosure are set forthbelow in weight percent:

Material Ex. 1 Ex. 2 Ex. 3 Ex. 4 Polymer 40-95  50-90 55-85 55-75Antimicrobial 4-49 10-40 20-38 25-35 nanoparticle Additive 0.001-30   0.001-18   0.002-12   0.002-11   Other material 0-30  0-20  0-18  0-15Material Ex. 5 Ex. 6 Ex. 7 Ex. 8 Polymer 50-95  50-85 55-80  55-65 Antimicrobial 5-40 15-35 25-35  28-33  nanoparticle Surfactant0.001-10    0.001-8    0.001-7    0.002-6    Coupling agent 0.001-10   0.001-8    0.001-7    0.002-6    Mica 0-20  0-15 1-15 5-12 Colorant 0-5 0-4 0.01-3    0.1-2   Tourmaline 0-15  0-15 1-15 5-12 Thinning agent0-20  0-18 1-15 5-14 Material Ex. 9 Ex. 10 Ex. 11 Ex. 12 PET or 40-7045-70 50-65  55-63  polyester Zinc 20-45 25-40 25-35  26-33 nanoparticle Surfactant 0.001-10   0.001-8    0.001-7    0.002-6   Coupling 0.001-10   0.001-8    0.001-7    0.002-6    agent Mica  0-20 0-15 1-15 5-12 Colorant 0-5 0-4 0.01-3    0.1-2   Tourmaline  0-15 0-15 1-15 5-12 Thinning agent  0-20  0-18 1-15 5-14

The masterbatch may be formed by mixing the components at a temperaturethat will not degrade or adversely affect the components of themasterbatch. Typically, the temperature is maintained below atemperature that will damage or burn off the one or more additivesand/or damage the polymeric material. In one non-limiting embodiment,the mixing temperature of the masterbatch is at least 10° C. above thecrystallization temperature of the polymetric component. In anothernon-limiting embodiment, the mixing temperature of the masterbatch isless than the boiling point of the polymetric component. In onenon-limiting example, the polymeric material in the masterbatch is orincludes PET, and the mixing temperature of the components of themasterbatch is 120-220° C., typically 130-200° C., more typically130-180° C., and still more typically 130-165° C.

After the components of the masterbatch are sufficiently mixed together,the masterbatch may be cooled and be formed into any suitable form(e.g., flakes, pellets, etc.). The one or more additives can beoptionally mixed with a portion or all of the antimicrobialnanoparticles prior to or after adding the antimicrobial nanoparticlesto the polymeric component. As can be appreciated, the polymericcomponent can be melted prior to the addition of the antimicrobialnanoparticles and/or the one or more additives when forming themasterbatch. The final masterbatch in solid form generally has little orno thinning agent (when used) in the solid masterbatch. During theformation of the solid masterbatch, most, if not all, of the thinningagent (when used) evaporates and/or degrades.

Non-limiting examples of formulations of the final masterbatchcomposition in accordance with the present disclosure are set forthbelow in weight percent:

Material Ex. 1 Ex. 2 Ex. 3 Ex. 4 Polymer 40-96 50-93 55-86 55-76Antimicrobial  4-49 10-40 20-38 25-35 nanoparticle Additive 0.001-30  0.001-18   0.002-12   0.002-11   Other material 0-5 0-4 0-3 0-2 MaterialEx. 5 Ex. 6 Ex. 7 Ex. 8 Polymer 50-96 50-86   55-82 55-66 Antimicrobial 5-41 15-36   25-36 28-34 nanoparticle Surfactant 0.001-11   0.001-9   0.001-8  0.002-7    Coupling agent 0.001-11   0.001-8    0.001-7 0.002-6    Mica  0-20  0-15    1-15  5-12 Colorant 0-5 0-4 0.01-3 0.1-2 Tourmaline  0-15  0-15    1-15  5-12 Thinning agent 0-5 0-4 0.01-20.01-1   Material Ex. 9 Ex. 10 Ex. 11 Ex. 12 PET or polyester 40-7245-72 50-66   55-64 Zinc nanoparticle 20-47 25-42 25-37   26-35Surfactant 0.001-11   0.001-9    0.001-8    0.002-7  Coupling agent0.001-11   0.001-9    0.001-8    0.002-7  Mica  0-20  0-15  1-15    5-12Colorant 0-5 0-4 0-3 0.01-2 Tourmaline  0-15  0-15  0-15    5-12Thinning agent 0-5 0-4 0-2 0.01-1

The masterbatch can be blended 120 with a second polymeric component toform the final fiber or device, or the masterbatch can be used to formthe fiber or device.

When the fiber or device is formed from a mixture of masterbatch and asecond polymeric component, the masterbatch and second polymericcomponent can be heated to melt together, or the masterbatch can beadded to the second polymeric component when the second polymericcomponent is already melted or vice versa. Typically, the masterbatchconstitutes about 2-50 wt. % (and all values and ranges therebetween) ofthe mixture and the second polymeric component constitutes about 50-98wt. % (and all values and ranges therebetween) of the mixture, moretypically the masterbatch constitutes about 2-25 wt. % of the mixtureand the second polymeric component constitutes about 75-98 wt. % of themixture, still more typically the masterbatch constitutes about 3-15 wt.% of the mixture and the second polymeric component constitutes about85-97 wt. % of the mixture, yet still more typically the masterbatchconstitutes about 4-12 wt. % of the mixture and the second polymericcomponent constitutes about 88-96 wt. % of the mixture, and even stillmore typically the masterbatch constitutes about 4-10 wt. % of themixture and the second polymeric component constitutes about 90-96 wt. %of the mixture.

Typically, the temperature of the mixture of the masterbatch and secondpolymeric component is maintained below a temperature that will damagethe polymeric material in the masterbatch or the second polymericcomponent. The second polymeric component can be formed of a single typeof polymer (e.g., polyester, PET, PA, PP, PBT, Aramid, PE, PC, ABS,etc.) or two or more different types of polymer. The type of polymerused to form the second polymeric component can be the same or differentfrom the polymeric component used in the masterbatch. In onenon-limiting embodiment, at least a portion or all of the secondpolymeric component is the same as a portion or all of the polymericcomponent in the masterbatch. In some embodiments, both the polymericcomponent in the masterbatch and the second polymeric component are orcontain a polyester.

The masterbatch and the second polymeric component are mixed at atemperature that will not adversely affect the components of themasterbatch and the second polymeric component (e.g., 120-350° C.,165-290° C., etc.). The second polymetric component can be formed of oneor more polymer materials. Typically, the temperature is maintainedbelow the temperature that will damage the polymeric component. Themixing process used to mix the masterbatch and the second polymericcomponent can be by a standard mechanical stirring process (e.g.,mechanical mixing, etc.). During the mixing process of the masterbatchand the second polymeric component, most, if not all, of the componentsof the masterbatch remain in the blended mixture. During the mixingprocess of the masterbatch and the second polymeric component,additional thinning agent can be added to the mixture; however, this isnot required. Also, during the mixing process of the masterbatch and thesecond polymeric component, additional surfactant and/or coupling agentcan be added to the mixture; however, this is not required.

The blended mixture is then extruded 130, spun into fibers 140,optionally stretched, and wound and/or cooled 150. During the finalformation of the fibers, the mixture is subjected to heat and otherconditions so that at least about 80% of the additive (e.g., couplingagent, surfactant, thinning agent) is removed (e.g., evaporated) orotherwise burned from the formed fiber, typically at least about 90% ofthe additive is removed or otherwise burned from the formed fiber, moretypically at least about 95% of the additive is removed or otherwiseburned from the formed fiber, still more typically at least about 99% ofthe additive is removed or otherwise burned from the formed fiber, andstill even more typically at least about 99.9% of the additive isremoved or otherwise burned from the formed fiber. Additives such ascolorant, mica, tourmaline, etc., typically at least partially remain inthe final formed fiber. For example, when colorant, tourmaline, and/ormica are included in the mixture used to form the final fiber, generallyat least 40% of the colorant, tourmaline, and/or mica remain in thefinal formed fiber, and typically at least 50% of the colorant,tourmaline, and/or mica remain in the final formed fiber. Generally, themixture is at a temperature above the softening point of the polymericcomponents in the mixture, and typically at or above the melting pointof the polymeric components in the mixture when the mixture is extrudedand/or spun into fiber during the fiber forming process.

The formed fibers generally include about 0.2-5 wt. % (and all valuesand ranges therebetween) antimicrobial nanoparticles, typically 0.5-3wt. % antimicrobial nanoparticles, and more typically 1-2 wt. % (e.g.,1.5 wt. %, etc.) antimicrobial nanoparticles. The formed fibers canoptionally include 0.1-2.5 wt. % (and all values and rangestherebetween) other materials (e.g., colorant, mica, tourmaline, etc.).Due to the surfactant and coupling agent in the mixture during the fiberforming process, the antimicrobial nanoparticles are uniformlydistributed throughout the formed fiber and the amount of agglomerationin the formed fiber is significantly reduced as compared to a fiber thatincludes antimicrobial nanoparticles without the use of surfactant andcoupling agent. The use of the surfactant and coupling agent in themixture during the fiber forming process results in less than 50% of theantimicrobial nanoparticles agglomerating in the formed fiber, andtypically results in less than 30% of the antimicrobial nanoparticlesagglomerating in the formed fiber. As such, the average density of theformed fiber along the length of the formed fiber does not vary by morethan 20%, typically no more than 10%, and more typically no more than5%.

The formed fibers can be interwoven, spun, or otherwise combined withone or more other fibers (e.g., natural fiber [cotton, wool, silk,linen, hemp, flax, etc.] synthetic fibers [rayon, polyester, nylon,mylar, glitter], and/or metallic fibers) to form a final fiber mixturethat can be used to form a thread that can be later used to form varioustypes of textiles (e.g., sheets, pillow cases, table clothes, towels,napkins, clothing, shoes, etc.) or other articles that are partially orfully formed from threads. As can be appreciated, the final thread canbe formed of 100% of the formed fiber. When the thread is formed of acombination of the formed fiber and one or more other fibers, the formedfiber generally constitutes about 2-90 wt. % (and all values and rangestherebetween) of the thread, typically 5-80 wt. % of the thread, moretypically 10-75 wt. % of the thread, and still more typically 30-70 wt.% of the thread. In one particular example, the thread contains at least30 wt. % of the formed fiber.

Referring now to FIG. 9, there is illustrated a flowchart for anothernon-limiting method for forming antibacterial fibers in accordance withsome non-limiting embodiments of the present disclosure. The formationof a separate masterbatch is eliminated from this method. The method 200includes melt blending 210 a polymeric component, antibacterialnanoparticles, and one or more additives. The antibacterialnanoparticles can optionally be mixed with the additive prior to addingto the polymeric component so that the antibacterial nanoparticles arecoated with the additive prior to being mixed with the polymericcomponent. Additional materials (e.g., thinning agent, colorant, mica,tourmaline, etc.) can optionally be added to the mixture. The additiveis typically present in an amount of 0.02-0.6 wt. % (and all values andranges therebetween) of the total mixture. The other materials, whenused, typically constitute about 0.01-15 wt. % (and all values andranges therebetween) of the total mixture.

Typically, the temperature is maintained below the temperature that willdamage or burn off the one or more additives. The blended composition isthen extruded 220, spun 230, and wound and/or cooled 240. During thefinal formation of the fibers, the mixture is subjected to heat andother conditions so that at least about 80% and typically about 90-100%of the additive is removed or otherwise burned from the formed fiber.The formed fiber generally includes about 0.2-5 wt. % (and all valuesand ranges therebetween) antimicrobial nanoparticles, typically 0.5-3wt. % antimicrobial nanoparticles, and more typically 1-2 wt. % (e.g.,1.5 wt. %, etc.) antimicrobial nanoparticles. The formed fiber generallyincludes little or no additive such as surfactant, coupling agent, andthinning agent (e.g., less than 0.5 wt. %, and typically less than 0.1wt. %). The formed fiber can optionally include colorant, mica,tourmaline, etc.

Other methods included within the scope of the present disclosureinclude the use of multiple masterbatches and/or multiple polymeraddition steps.

In some embodiments, a special-shaped antibacterial fiber includesnanometer-scale antibacterial powder (e.g., zinc antibacterial powder,etc.) and polyester. The cross section of the antibacterial fiber may beany non-circular cross-sectional shape such as, but not limited to,clover-shaped, cross-shaped, oval-shaped, or some other non-circularcross-sectional shape.

The median diameter (D50) of the antibacterial nanoparticles may be lessthan or equal to 0.1 μm, including within the range of from about 50 nmto about 200 nm (and all values and ranges therebetween). In aparticular non-limiting embodiment, the D50 of the antibacterialnanoparticles is about 60-80 nm. It has been found that antibacterialnanoparticles above 200 nm and below 50 nm do not distribute evenly inthe formed fiber.

In particular non-limiting embodiments, a cross-shaped antibacterialfiber according to the disclosure is prepared using the following steps:

Step 1: A functional masterbatch is prepared by mixing zincnanoparticles, additives, and polyester according to the specific massratio of different purposes. The mass ratio of the zinc nanoparticles tothe polyester is 15:80 to 40:55 (and all values and rangestherebetween). The percentage of additive to the total mass of thefunctional masterbatch is 0.001-10 wt. % (e.g., 0.002-5 wt. %). The zincnanoparticles, additives, and polyester may be stirred and mixed at130-290° C., and then granulated to obtain the functional masterbatch.In particular non-limiting embodiments, the masterbatch contains 15-40wt. % zinc nanoparticles, and typically 20-38 wt. %, and more typically25-30 wt. %.

Step 2: The special-shaped antibacterial fiber is prepared by mixingtogether and melting the functional masterbatch of Step 1 and additionalpolyester. The mixture is formed by blending and melting together thefunctional masterbatch with the polyester chips such that the chips ofthe masterbatch constitute 4-12 wt. % of the total mixture. The mixturecan then be spun into fibers using standard technology used to formpolymer fibers.

Zinc nanoparticles in the formed fibers have good dispersibility in thefibers. The additives are used to facilitate in the zinc nanoparticlesbeing uniformly mixed and dispersed in the melted polyester. Theadditives can also be used to improve the spinnability of the materialto form the final fiber.

The masterbatch and/or the mixture of masterbatch and polymer can havecoloring added to the mixture to color the fiber without adverselyaffecting the antibacterial properties of the fiber, nor the uniformdispersal of the nanoparticles in the fiber. Other materials such asmica, tourmaline, etc., can be added to improve the texture of thefiber.

In one non-limiting embodiment, the additive that is included in themixture used to form the fiber includes one or more surfactants and/orone or more coupling agents. In some embodiments, both the surfactantand the coupling agent are included in the mixture used to form thefiber.

A surfactant can be optionally coated on the surface of theantibacterial nanoparticle (e.g., zinc nanoparticle powder) prior tomixing the antibacterial nanoparticle with the polymer; however, this isnot required. The surfactant is used to increase the surface activityand fluidity of the nanoparticle powder, prevent the oxidation of thenanoparticle powder, and/or inhibit or prevent weakening of theantibacterial effect of the nanoparticle powder. The one or moresurfactants can be selected from anionic surfactants, cationicsurfactants, non-ionic surfactants, and any combination of two or morethereof.

Non-limiting examples of surfactants include stearic acid, sodiumdodecyl sulfonate surfactants, quaternary ammonium surfactants, aminoacid surfactants, betaine surfactants, fatty acid glyceride estersurfactants, fatty acid sorbitan surfactants, lecithin surfactants,Tween™ series surfactants, and polysorbate surfactants. Combinations oftwo or more surfactants may also be utilized.

The coupling agent (e.g., silane coupling agent) is used to facilitatein the dispersion of the nanoparticle powder in the melted polymermixture prior to and/or during fiber formation and/or inhibit or preventagglomeration of the nanoparticle powder in the melted polymer mixtureprior and/or during fiber formation.

The coupling agent can be selected as silicon silane coupling agents,such as silane and/or titanate. Non-limiting examples of coupling agentsinclude silane coupling agent A-150, silane coupling agent A-151, silanecoupling agent A-171, silane coupling agent A-172, silane coupling agentA-1100, silane coupling agent A-187, silane coupling agent A-174, silanecoupling agent A-1891, silane coupling agent A-189, silane couplingagent A-1120, silane coupling agent KH-550, silane coupling agentKH-560, silane coupling agent KH-570, silane coupling agent KH-580,silane coupling agent KH-590, silane coupling agent KH-902, silanecoupling agent KH-903, silane coupling agent KH-792, and at least one ofphenyltrimethoxysilane, phenyltriethoxysilane, methyltriethoxysilane,titanate coupling agent 101, titanate coupling agent 102, and titanatecoupling agent 105. Combination of two or more coupling agents may alsobe utilized.

Nanoparticles have a tendency to agglomerate during the mixingprocesses. Agglomeration prevents nanoparticles from being uniformlydispersed in the melted polymer and the formed fiber. However, the useof a surfactant and/or a coupling agent increases the surface activityand fluidity of the nanoparticles, inhibits or prevents oxidation,and/or inhibits or prevents weakening the antibacterial effect of thenanoparticles. The dispersity of nanoparticles in the melted polymer isenhanced and the agglomeration of the nanoparticles during mixing isreduced or prevented, so that the nanoparticles are evenly distributedin the melted polymer and formed fiber.

The mixing techniques used to mix the masterbatch with the additionalpolymer material are not particularly limited. In some embodiments, thenanoparticles, additive, and polymeric component are sequentially mixedin a high-mixer according to a process flow.

Stirring speeds of 100±10 r/min. and a stirring time of 1-10 min. may beused.

The masterbatch may be stirred and mixed with a second polymericcomponent (which may be the same as or different from the firstpolymeric component). The mixed raw material may be added into a screwextruder and spun by a special spinneret such as a clover and a cross,so as to obtain a special-shaped zinc antibacterial fiber with a crosssection shape such as a clover and/or a cross.

In some non-limiting embodiments, the spinning speed is 1000-1500 m/min.The spinning may use a spinneret having a diameter of 0.2-0.8 mm.

The spun fibers may be wound and cooled (e.g., blow cooled).

The winding speed may be 950-1450 m/min.

Blow cooling may be horizontal blow cooling, and the blowing temperaturemay be 20-30° C.

In some non-limiting embodiments, the nanoparticles have a lighter colorwhich simplifies dyeing and processing. Zinc, for example, has a lightcolor.

The substantially uniform distribution of the nanoparticles in thefibers beneficially reduces the likelihood of the nanoparticles fallingout in subsequent printing, dyeing and washing treatment, ensuring thestability and antibacterial durability of the fibers.

Compared to fibers with circular-shaped cross sections, fibers withhigher surface areas exhibit good moisture absorption, quick drying,softness, resilience, and smoothness.

In some non-limiting embodiments, the metal nanoparticles are added tothe polymer without the need for chemical modifiers. The preparationmethod of the fiber with reduced or eliminated chemical modifiersshortens the process flow, reduces the equipment and process investment,reduces the cost, and is suitable for large-scale industrial production.

The metal nanoparticles are fine particles, thus agglomeration has beenfound to occur in the absence of additive(s). Therefore, a surfactantand/or a coupling agent can be used to increase the surface activity andfluidity of nanoparticles, thereby ensuring dispersion, preventingagglomeration, and evenly distributing the nanoparticles in thepolymeric component.

Composite clover-shaped cross section fibers and other special-shapedfibers have excellent properties that circular fibers do not have andincrease the surface area of the fiber. Textiles formed from the fibershave good antibacterial properties and moisture absorption, are fastdrying, UV resistant, soft, resilient, and smooth. The compositecompositions of the present disclosure are suitable for, but not limitedto, various shapes of fiber cross sections: clover, cross, hollow, flat,triangular, dumbbell, and the like. Hollow fibers (fiber having one ormore cavities along the length of the fiber) have been found to bettermimic the feel and softness of cotton fibers and other natural fibers.

EXAMPLE A

(1) Nano-zinc powders, polyester chips, silane coupling agent, andsurfactant were melted and mixed in a high shear mixer in sequenceaccording to the technological process at 150° C. Thinning agent wasoptionally added to the mixture to obtain a target mixing viscosity. Thecomposition was fully mixed and evenly stirred, and then granulated intoa granulator to make the functional masterbatch. Based on the total massof the functional masterbatch, the mass percentage of zinc powder was20-30 wt. % and the silane coupling agents and surfactants constituted0.001-10 wt. %.

(2) The functional masterbatch and polyester chips were added into aspinning box, melted and mixed at 220° C., while stirred to ensuremelting and even mixing and to produce mixed raw materials. The weightratio of the polyester chips to the functional masterbatch was about10:1 to 15:1.

(3) When the mixed material was added to the screw extruder, thetemperature in the heating box of the screw extruder was 260° C., andthe mixed material was heated slowly. Zinc antibacterial fiber withcross-shaped cross section was prepared by spinning with a cross-shapedspinneret having an aperture size of 0.35 mm.

(4) The obtained zinc antibacterial fibers with clover- and cross-shapedcross sections were wound and cooled by blowing.

The antibacterial activity of the zinc antibacterial fibers and the zincantibacterial fibers after washing 100 times were tested.

The results showed that the antibacterial rate of the zinc antibacterialfibers to S. aureus (>95%), E. coli (>95%) and C. albicans (>90%) werehigh.

After 100 industrial washings, the bacteriostatic rates of S. aureus(>95%), E. coli (>95%), and C. albicans (>80%) remained high.

EXAMPLE B

(1) This aspect was similar to Example 1, the difference being,according to the total mass of functional masterbatch, the mass percentof nanometer zinc powder was 25%, the mass percent of silane couplingagent and surfactant was 10%.

(2) This aspect was similar to Example 1, the difference being that thetemperature was 230° C.

(3) This aspect was similar to Example 1, the difference being that thetemperature of the heating box assembly of the screw extruder was 270°C.

(4) The above-mentioned special-shaped zinc antibacterial fibers, withclover- and cross-shaped cross sections, were wound and cooled bycross-blowing at 25° C.

The antibacterial activity of the zinc antibacterial fiber and the zincantibacterial fiber after 100 washings were tested.

The results showed that the antibacterial rate of zinc antibacterialfiber to S. aureus (>95%), E. coli (>95%) and C. albicans (>90%) washigh.

After 100 industrial washings, the bacteriostatic rate of S. aureus(>95%), E. coli (>95%), and C. albicans (>80%) remained high.

EXAMPLE C

(1) 200-350 kg. of nano-zinc powders and 590-795 kg. PET chips where drymixed together for about 2-20 minutes until the chips and powder aregenerally evenly mixed together.

(2) Silane coupling agent and surfactant and optionally other materials(e.g., colorant, mica, thinning agent, tourmaline) are added to themixture of nano-zinc powder and PET chips. The silane coupling agent andsurfactant and optionally other materials can be added to the mixture ofnano-zinc powder and PET chips prior to, during, or after the PET hasbeen melted. About 2-10 kg. of silane coupling agent and surfactant andoptionally about 1-120 kg. of thinning agent are used. About a 0.8:1 to1.2:1 weight ratio of silane coupling agent to surfactant is used.

(3) The mixture of nano-zinc powder and PET chips is heated to 165° C.to begin the melting of the PET chips. The silane coupling agent andsurfactant and optionally other materials can be added to the mixture ofnano-zinc powder and PET chips prior to, during, or after the PET hasbeen melted.

(4) After all of the components of the masterbatch are mixed together(e.g., high shear mixer, etc.), the mixture is heated from 165° C. toabout 250-350° C. over a time period of about 10-60 minutes.

(5) After the mixture has been heated to the desired temperature, themixture can then be extruded, cooled, and then chopped onto pieces ofmasterbatch.

After the masterbatch is formed, it can be mixed with additional polymerto form fibers or various types of polymer devices.

When antimicrobial fibers are to be formed, the chips of masterbatch aremixed with additional PET chips. The masterbatch chips constitute about3-10 wt. % of the mixture. The mixture is melted together at atemperature of about 200-350° C. The heated mixture is then formed intofibers. The method for forming the fibers can be by standardfiber-forming methods (e.g., extrusion, spinneret, blowing technology,etc.). The formed fibers generally include about 1.6-2.5 wt. % nano-zincpowder.

The formed fibers can then be formed into thread for use in fully orpartially forming various types of textile, etc. The formed thread canbe combined with 1-15 wt. % (and all values and ranges therebetween)modal to form a softer fiber.

In one nonlimiting embodiment, antimicrobial sheets can be formed from20-100% (and all values and ranges therebetween) antimicrobial fibersand 0-80% (and all values and ranges therebetween) other fibers (e.g.,cotton fibers, silk fibers, polymer fibers, etc.). In one particularnon-limiting embodiment, sheets are formed of 20-30% antimicrobialfibers and the balance cotton fibers. The total content of nano-zincpowder in the sheets are about 0.2-0.6 wt. %.

The cross-shaped zinc antibacterial fiber in accordance with the presentdisclosure exhibits good antibacterial performance, high antibacterialrate against S. aureus, E. coli and C. albicans, and no reduction inantibacterial rate against S. aureus and E. coli after 100 washings.Meanwhile, due to the cross-shaped cross section of the zincantibacterial fiber, the zinc antibacterial fiber has goodhygroscopicity, fast drying resistance, ultraviolet resistance,flexibility, resilience, smoothness, and makes sweat evaporate rapidly,which is not conducive to the survival of bacteria. Compounded with zincantibacterial function, the moisture absorption and antimicrobialproperties of the fiber do not interfere with each other and promoteeach other, and the hydrophilic, moisture absorption, and quick dryingcharacteristics are not affected by the washing times of the fabric.Additionally, the preparation method of the cross-shaped zincantibacterial fiber not only reduces the use of chemical modifiers, butis also simple, feasible, and suitable for large-scale industrialproduction.

It will thus be seen that the objects set forth above, among those madeapparent from the preceding description, are efficiently attained, andsince certain changes may be made in the constructions set forth withoutdeparting from the spirit and scope of the disclosure, it is intendedthat all matter contained in the above description and shown in theaccompanying drawings shall be interpreted as illustrative and not in alimiting sense. The disclosure has been described with reference topreferred and alternate embodiments. Modifications and alterations willbecome apparent to those skilled in the art upon reading andunderstanding the detailed discussion of the disclosure provided herein.This disclosure is intended to include all such modifications andalterations insofar as they come within the scope of the presentdisclosure. It is also to be understood that the following claims areintended to cover all of the generic and specific features of thedisclosure herein described and all statements of the scope of thedisclosure, which, as a matter of language, might be said to fall therebetween. The disclosure has been described with reference to thepreferred embodiments. These and other modifications of the preferredembodiments as well as other embodiments of the disclosure will beobvious from the disclosure herein, whereby the foregoing descriptivematter is to be interpreted merely as illustrative of the disclosure andnot as a limitation. It is intended to include all such modificationsand alterations insofar as they come within the scope of the appendedclaims.

What is claimed:
 1. A textile comprising antimicrobial fibers, at leastone of said antimicrobial fibers comprising: a polymer matrix;antimicrobial nanoparticles dispersed substantially uniformly throughoutthe polymer matrix, said substantially uniform dispersion of saidantimicrobial nanoparticles in said antimicrobial fibers at leastpartially a result of a mixture of a) polymer used to form said polymermatrix, b) antimicrobial nanoparticles, and c) surfactant and/orcoupling agent prior to the formation of said antimicrobial fibers. 2.The textile of claim 1, wherein said mixture includes both saidsurfactant and said coupling agent.
 3. The textile as defined in claim1, wherein the antimicrobial nanoparticles include one or more metalmaterials selected from the group of zinc metal, copper metal, silvermetal, iron metal, zinc oxide, copper oxide, silver oxide, iron oxide,zinc salt, copper salt, silver salt, and iron salt.
 4. The textile asdefined in 1, wherein said polymer used to form said polymer matrixincludes one or more polymer materials selected from the groupconsisting of a polyester, a polyamide, a polyolefin, a polycarbonate,and an acrylonitrile butadiene styrene polymer.
 5. The textile asdefined in claim 4, wherein said polymer used to form said polymermatrix includes the polyester, said polyester includes polyethyleneterephthalate.
 6. The textile as defined in claim 1, wherein saidantimicrobial nanoparticles have a median particle size of less than orequal to 0.2 μm.
 7. The textile as defined in claim 1, wherein saidantimicrobial fibers comprise about 0.5-12 wt. % of said antimicrobialnanoparticles.
 8. The textile as defined in claim 1, wherein saidantimicrobial fibers have a cross section shape selected from the groupconsisting of a clover, cross, hollow cylinder, triangle, and dumbbell.9. The textile as defined in claim 1, wherein said mixture includes saidsurfactant, said surfactant includes one or more compounds selected fromthe group consisting of stearic acid, sodium dodecyl sulfonatesurfactants, quaternary ammonium surfactants, amino acid surfactants,betaine surfactants, fatty acid glyceride ester surfactants, fatty acidsorbitan surfactants, lecithin surfactants, and Tween™ seriessurfactants.
 10. The textile as defined in claim 1, wherein said mixtureincludes said coupling agent, said coupling agent includes a silaneand/or titanate coupling agent.
 11. The textile as defined in claim 10,wherein said coupling agent includes one or more compounds selected fromthe group consisting of silane coupling agent A-150, silane couplingagent A-151, silane coupling agent A-171, silane coupling agent A-172,silane coupling agent A-1100, and silane coupling agent. Agent A-187,silane coupling agent A-174, silane coupling agent A-1891, silanecoupling agent A-189, silane coupling agent A-1120, silane couplingagent KH-550, silane coupling agent KH-560, silane coupling agentKH-570, silane coupling agent KH-580, silane coupling agent KH-590,silane coupling agent KH-902, silane coupling agent KH-903, silanecoupling agent KH-792, phenyltrimethoxysilane, phenyltriethoxysilane,methyltriethoxysilane, titanate coupling agent 101, titanate couplingagent 102, and titanate coupling agent
 105. 12. The textile as definedin claim 1, wherein said antimicrobial fibers include mica, colorant,tourmaline, and/or aromatic material.
 13. The textile as defined inclaim 1, wherein said textile is selected from the group consisting of aclothing, bedding, towels, cloths, rags, mops, shoes and other types offootwear, caps, hats, luggage, purses, backpacks, carrying cases,furniture fabric, curtains, awnings, tents, umbrellas, furniture covers,grill covers, laundry containers, storage containers, rugs, carpeting,pillow covers, blankets, throws, seat covers, bandages, straps, rope,twine, yarn, string, gowns, scrubs, masks, bandages, dressings, pillows,life jackets, bathmats, pads, diapers, wipes, sleeping bags, pet beds,pet toys, canvas products, and any other device or material that isfully or partially formed from threads and/or fabric.
 14. The textile asdefined in claim 1, wherein said textile is at least partially formedfrom threads of material, at least a plurality of said threads used toat least partially form said textile includes said antimicrobial fibers,said threads that include said antimicrobial fibers formed of at least10 wt. % of said antimicrobial fibers.
 15. An antimicrobial fibercomprising: a polymer matrix; antimicrobial nanoparticles dispersedsubstantially uniformly throughout the polymer matrix, saidsubstantially uniform dispersion of said antimicrobial nanoparticles insaid antimicrobial fibers at least partially a result of a mixture of a)polymer used to form said polymer matrix, b) antimicrobialnanoparticles, and c) surfactant and/or coupling agent prior to theformation of said antimicrobial fibers.
 16. The antimicrobial fiber asdefined in claim 15, wherein said mixture includes both said surfactantand said coupling agent.
 17. The antimicrobial fiber as defined in claim15, wherein said antimicrobial nanoparticles include one or more metalmaterials selected from the group of zinc metal, copper metal, silvermetal, iron metal, zinc oxide, copper oxide, silver oxide, iron oxide,zinc salt, copper salt, silver salt, and iron salt.
 18. Theantimicrobial fiber as defined in claim 15, wherein said polymer used toform said polymer matrix includes one or more polymer materials selectedfrom the group consisting of a polyester, a polyamide, a polyolefin, apolycarbonate, and an acrylonitrile butadiene styrene polymer.
 19. Amethod for forming antimicrobial fibers, the method comprising: spinninga heated mixture to form spun antimicrobial fibers, said heated mixturecomprising antimicrobial nanoparticles, polymeric component, and atleast one additive selected from the group consisting of surfactant andcoupling agent.
 20. The method as defined in claim 19, furthercomprising the step of winding, stretching and/or cooling said spunfibers.
 21. The method as defined in claim 19, wherein said at least oneadditive includes both surfactant and coupling agent.
 22. The method asdefined in claim 19, wherein said antimicrobial nanoparticles includeone or more metal materials selected from the group of zinc metal,copper metal, silver metal, iron metal, zinc oxide, copper oxide, silveroxide, iron oxide, zinc salt, copper salt, silver salt, and iron salt.23. The method as defined in claim 19, wherein said polymer componentincludes one or more polymer materials selected from the groupconsisting of a polyester, a polyamide, a polyolefin, a polycarbonate,and an acrylonitrile butadiene styrene polymer.
 24. The method asdefined in claim 19, wherein said antimicrobial fibers have a crosssection shape selected from the group consisting of a clover, cross,hollow cylinder, triangle, and dumbbell.
 25. A method for forming amasterbatch for use in mixing with another polymer to form anantimicrobial fiber, the method comprising: blending a mixturecomprising antimicrobial nanoparticles, a polymeric component, and atleast one additive selected from the group consisting of surfactants andcoupling agents; and granulating said blended mixture to form granulatedpieces of said masterbatch.
 26. The method as defined in claim 25,wherein said step of blending is at a temperature of about 100-350° C.27. The method as defined in claim 25, wherein said step of blending isat a temperature of about 200-300° C.
 28. The method as defined in claim25, wherein said step of blending is at a temperature of about 210-290°C.
 29. The method as defined in claim 25, wherein said antimicrobialnanoparticles constitute about 4-49 wt. % of said masterbatch, saidpolymeric component constitutes about 40-95 wt. % of said masterbatch.30. The method as defined in claim 25, wherein said at least oneadditive constitutes about 0.001-30 wt. % of said masterbatch.
 31. Themethod as defined in claim 25, wherein said antimicrobial nanoparticlesinclude one or more metal materials selected from the group of zincmetal, copper metal, silver metal, iron metal, zinc oxide, copper oxide,silver oxide, iron oxide, zinc salt, copper salt, silver salt, and ironsalt.
 32. The method as defined in claim 25, wherein said polymericcomponent includes one or more polymer materials selected from the groupconsisting of a polyester, a polyamide, a polyolefin, a polycarbonate,and an acrylonitrile butadiene styrene polymer.
 33. A method for formingantimicrobial fibers, the method comprising: extruding a mixturecomprising masterbatch particles and polymer particles; spinning theextruded mixture into spun fibers; and, wherein said masterbatchparticles comprise antimicrobial nanoparticles, a masterbatch polymer,and at least one additive selected from the group consisting ofsurfactants and coupling agents.
 34. The method as defined in claim 33,wherein said step of extruding is at a temperature about 200-350° C. 35.The method as defined in claim 34, wherein said mixture comprises about2-20 wt. % of said masterbatch particles and about 80-98 wt. % of saidpolymer particles.
 36. An antimicrobial thread comprising antimicrobialfibers and non-antimicrobial fibers, said antimicrobial fibersconstitute about 15-90 wt. % of said antimicrobial thread, saidnon-antimicrobial fibers constitute about 10-85 wt. % of saidantimicrobial thread, wherein said antimicrobial fibers formed of apolymer matrix having antimicrobial nanoparticles dispersedsubstantially uniformly throughout said polymer matrix, saidsubstantially uniform dispersion of said antimicrobial nanoparticles insaid antimicrobial fibers at least partially a result of a mixture of a)polymer used to form said polymer matrix, b) antimicrobialnanoparticles, and c) surfactant and/or coupling agent prior to theformation of said antimicrobial fibers, and wherein saidnon-antimicrobial fibers include one or more materials selected from thegroup consisting of cotton fibers, wool fibers, silk fibers, linenfibers, hemp fibers, flax fibers, rayon fibers, polyester fibers, nylonfibers, mylar fibers, glitter fibers and metallic fibers, saidnon-antimicrobial fibers absent antimicrobial nanoparticles.
 37. Theantimicrobial thread as defined in claim 36, wherein less than 1% ofsaid antimicrobial nanoparticles in said antimicrobial fibers leach fromsaid antimicrobial fibers after said antimicrobial thread has beensubjected to one standard wash cycle.
 38. The antimicrobial thread asdefined in claim 36, wherein less than 1% of said antimicrobialnanoparticles in said antimicrobial fibers leach from said antimicrobialfibers after said antimicrobial thread has been subjected to 100standard wash cycles.